Unsaturated ethers of hydroxydihydronordicyclopentadiene



Patented Jan. 29, 1946 UNITED STATES PATENT UNSATURATED ETHERS OF HYDROXYDI- HYDRONORDIOYOLOPENTADIENE Herman A. Bruson,'Philadelphia, 'Pa., assignor to The Resinous Products & Chemical Company, Philadelphia, Pa., a corporation of Delaware N6 Drawing. Application March 13, 1944,

Serial No. 520314 e 23 Claims. (omen-611) This invention relates to ethers of hydroxydihydronordicyclopentadiene and an unsaturated monohydric alcohol.

This application is .a continuation-in-part of my copending application Serial No. 476,640, filed February 20, 1943.

According to this invention, an unsaturated monohydric alcohol, ROH, wherein R is an unsaturated organic residue aliphatically bound to the hydroxyl group, is condensed with dicyclopentadiene in the presence of an acidic condensin: agent as catalyst whereby addition or components of the alcohol to the terminal endomethylene double bond of the dicyclopentadiene occurs with a simultaneous molecular rearrangetion, (A) representing the more probable configuration oi the two posslbleisomers (A) and (B).

The product is characterized by the presence of the ether group in an endoethylene cyclopentano cycle which forms one terminal cycle of the nordicyclopentenyl system, while the opposite terminal cycle consists of a flve-membered ring having an olefinic linkage.

The dihydronordicyclopentacliene system is delined by the following structure:

wherein Call; is a propenylene group which in conjunction with the adjoining carbon atoms forms a cyclopenteno ring, as one terminal cycle.

As is evident from consideration of the above Iormulae, a functional group or substituent is attached at the point marked a to a secondary carbon atom which is flanked by a methylene group and a tertiary carbon atom in an endoethylene cyclopenteno group carrying the propenylene group which forms the cyclopenteno ring therewith,

The unsaturated monohydric alcohols used may be olefinic or acetylenic in character. Typical alcohols of this class include, for example, allphatic and arylaliphatic alcohols, including allyl, methallyl, crotyl, 2-chlorallyl, propargyl, or cinnamyl alcohols, methyl vinyl carbinol, dimethyl ethy'nyl carbinol, geraniol, citronellol, oleyl alcohol, allyloxyethanol,

CH2=CH--CHc-OCH2CH2OH beta- (allyloxyethoxy) -ethanol,

CH2=CH-CHeO-CH2CH2OCHaCI-I2OH the various pentenyl, hexenyl, octenyl, nonenyl, dodecenyl, tridecenyl and higher alcohols containirig at least one double bond, and cycloaliphatic alcohols, including cyclohexenol, tetrahydro-N-benzyl alcohol, 2,5-endomethylene-tetrahydro-AJ-benzyl alcohol, ii-methyl-tetrahydro-n benzyl alcohol, G-propyl-tetrahydro-A benzyl alcohol, 2,5-endomethylene-A -6-methyl tetrahydrobenzyl alcohol, hydroxydihydronordicyclopentadiene, hydroxydihydronortricyclopentadiene, and the like.

Among the acidic condensing agents or catalysts which serve to promote the addition-rearrangement reaction are boron triiiuoride and its coordination complexes with oxygenated compounds, sulfuric acid, its acid esters such as ethyl acid sulfate, aromatic sulfonic acids such as toluene sulfonic acid, aliphatic sulfonic acids such as butyl sulfonic acid, acidic salts such as zinc chloride, stannic chloride, titanium tetrachloride, arltimonic chloride, aluminum chloride, ferric chloride; acidic siliceous clays such as that sold under the t1 ade names of Tonsil or Atapulgas," etc. i

As examples of the coordination complexes of boron trifluoricle, there may be cited those with ethers, typified by BF3.C2H5OC2H5 and BF3.C4H9OC4H9; with carboxylic acids, typified by BF3.2CH3COOH; with carboxylic esters, typifled by BF3.2CH3COOC2H5; with ketones, typified by BF3.CH3COCH3; with alcohols, typified by BF3.2C4H9OH; and with water, which may be represented by BF3.(H2O):,- a: being usually one or two.

lhe preferred catalysts are sulfuric acid and boron trifiuoride or its coordination complexes.

catalyst on the weight of the dicyclopentadiene up to and exceeding a molecular equivalent of the catalyst per mol of dicyclopentadiene used. The catalysts need not be used under anhydrous conditions. In fact, the presence of water in small amounts often increases the r of the re ction.

The addition-rearrangement reaction may be initiated by mixing the components and catalyst at temperatures even as low as C. in some cases,

or at room temperature, or at elevated tempera- I tures. While it is generally desirable to keep the temperature low at the start, the reaction may be carried to completion or accelerated by raising the temperature or by continuing the reaction for a long time at a relatively low temperature. Temperatures as high as 100 C. to 150 C. may thus be used, the upper temperature being limited by the cracking tendency of the dicyclopentadiene to rev rt to monomeric cyclopentadiene. The reaction range of about 50 C. to 145 C. is generally the most useful and is to be preferred. The reaction can be controlled by the rate of mixing the reactants and by the use of a solvent or diluent, such as a hydrocarbon solvent including petroleum ethers or petroleum naphthas, or chlorinated hydrocarbon such as carbon tetrachloride, ethylene dichloride, tetrachlorethane and the like.

After the reaction has been carried to the desired point, the acidic condensing agent is removed as by washing with water or neutralization with an alkali, or both. The reaction product may then be distilled in many cases or otherwise purified, as by treatment with decolorizing clay or carbon, stripping, extraction, etc.

The following examples illustrate this invention, it being understood that the proportions, temperatures and time can be varied over a wide range without departing from the spirit or the invention.

Example 1 To a stirred mixture of 390 g. of di'cyclopentadiene and 204 g. of beta-allyloxyethanol, CH2=HCH2O-CH2CH2OH, heated to 55 0.,

there was added dropwise 14.- g. of boron tri-' fiuoride-dibutyl ether complex, BF3.O (C4H9) a. The temperature of the mixture was then gradually raised to 125-130 C. and held there for six and one-quarter hours with continuous stirring, A

dark oil was obtained which was washed with hot,

dilute sodium hydroxide solution and then with water. The oil was separated, dried, and distilled in vacuo.

The allyloxyethoxy-dihydronordicyclopentadiene having the probable formula Upon redistillation, the pure product distilled at 125 C./3 mm.

2,ses,eos

Example 2 To 116 g. of allyl alcohol cooled to 0 C., 25 of 98% sulfuric acid was gradually added at such a rate that the temperature did not exceed 5 C. The solution was allowed to come to room temperature and was then mixed with 132 g. of dicyclopentadiene. This mixture was stirred and gradually heated on a steam bath under a reflux condenser. After the initial exothermal reaction, which'carried the temperature of the mixture to 108 C., was over, the mixture was stirred for three hours at -100 C., and poured into water. n oil layer separated. The oil was mixed with an equal volume of toluene, stirred with 5 g. of powdered lime, and filtered. The filtrate was distilled under reduced pressure.

The allyloxy-dihydronordicyclopentadiene dis tilled at 92-95 C./2 mm. as a colorless oil having a pleasant, flowery odor. The yield was 106 g. Upon redistillation it boiled at 118 C. /12 mm. and possessed the following constants N 1.5000; d4 09960..

Example 3 A stirred mixture of 93g. of 2-chloro-allyl alcohol and 145 g. of dicyclopentadiene was heated to 55 0., and 10 g. of BF5.0(C4H9)2 added. The exothermal reaction carried the temperature to 90 C. at which point cooling was applied. The

mixture was then stirred and heated for six hours at 0., washed with hot dilute soda solution, then with water, dried, and distilled in vacuo.

The 2-chloro-allyloxy-dihydronordicyclopentadlene on OH: or. CE Cl UH:

distilled over between 97 and 117 C./1 mm. as a colorless oil in a yield of 151 g.

Upon redistillation the pure compound boiled at C./9 mm.

Example 4 To a stirred mixture of 268 g. of technical oleyl alcohol (Oceno1") and 160 g. of dicyclopentadlene heated to 60 C. there was radually added 7. g. of BF3.O(C2H5)2. The mixture was gradually heated to 125-l30 C. and held, thereat for six hours. The product was then washed with hot dilute sodium hydroxide solution, then with water, filtered, and distilled in vacuo. The oleyloxy dihydronordicyclopentadiene distilled over between 237 and 245 C./1 mm. as a pale yellow oil in a yield of 176 g.

Example 5 (a) A stirred mixture of 156 g. of citronellol, 198 g. of dicyclopentadiene and 7 g. of dihydroxyfluoboric acid, BF3.2H2O, was heated at 120-125 C. for six and one-quarter hours. The product was then stirred with 20 g. of powdered sodium carbonate and 5 g. of water for one hour, then filtered and distilled in vacuo. The citronellyloxy-dihydrondrdicyclopentadiene distilled over between and 180 C./1-2 mm. as a colorless oil in a yield of 1'70 g. Upon redistillation the pure compound boiled at 165 C./2 mm.

(b) In the same manner geranlol, used in place of the citronellol above, yielded geranyloxydihydronordicyclopentadiene as an oil boiling at c./2 mm.

Example 6 A mixture or 134 g. of cinnamyl alcohol. 132 g. of dicyclopentadiene and 25 g. of

" BF3.C2H5OC2H5 distilled over as a pale l79-182 C./2 mm.

v Example 7 g. of BF3.C4H9OC4H9 complex was added dropwise to 62 g. of 2,5-endomethylene-A -tetrahydro benzyl alcohol and 66.8 g. of dicyclopentayellow, viscous oil at diene at 25-27 C. during the course of two minutes. The mixture was stirred and heated at 90-95 C. for six hours. It was then washed with dilute sodium hydroxide solution, then with water, dried and'distilled. The product distilled over as practically a. colorless oil, boiling at 145- 155" can-2; mm. V

The unsaturated ethers of hydroxydihydronordicyclopentadierie, R-O-CmHn, wherein R is an unsaturated group, polymerize when heated with 5% benzoyl peroxide at 100 (2. to viscous oils. They also polymerize to viscous liquids when blown with air at 80-100 C. The resulting polymers, as well as the unpolymerized ethers themselves, when applied as coatings, rapidly absorb oxygen from the air to form varnish-like fi m particularly in the presence of siccatives. They can, therefore, be used alone or in conjunction with natural fatty glycerides such as, for example, linseed oil, tung oil, soya bean oil, or dehydrated castor oil, or with alkyd resinsto yield varnishes. Iclaimr 1. An acid-catalyzed, addition-rearrangement product of an unsaturated alcohol and dicyclopentadiene, said product being an ether or the The cinnamyloxy-dihydronordicyclopentadiene unsaturated alcohol and hydroxydihydronordicyclopentadiene, in which the alcohol residue is attached through oxygen to a secondary carbon atom flanked by a methylene group and a tertiary carbon atom in an endoethylene cyclopentano group carrying a propenylene group which forms a cyclopenteno ring therewith.

2. An acid-catalyzed, addition rearrangement product of an unsaturated monohydric alcohol and dicyclopentadiene, said product being an ether having the formula ROC10H13 wherein R is the hydrocarbon residue of an unsaturated alcohol and -C1oH13 is the dihydronordicyclopentadienyl radical wherein the oxygen is attached to a secondary carbon atom flanked by a methylene group and a tertiary carbon atom in an endoethylene cyclopentano group carrying a propenylene group which forms a cyclopenteno ring therewith.

3. An acid-catalyzed, addition-rearrangement product of an unsaturated aliphatic alcohol and dicyclopentadiene, said product being an ether of the unsaturated aliphatic alcohol and hy- 'droxydihydronordicyclopentadiene, in which the alcohol residue is attached through oxygen to a secondary carbon atom flanked by a methylene group and a tertiary carbon atom in an endoethylene cyclopentano group carrying a propenylene group which forms a cyclopenteno ring therewith.

4. An acid-catalyzed, addition-rearrangement product or an unsaturated olefinic monohydric alcohol and dicyclopentadiene, said product being an elilahler or the unsaturated olefinic monohydric alco 0 through oxygen to a secondary carbon atom flanked by a methylene group and a tertiary carbon' atom in an endoethylene cyclopentano group carrying a propenylene group which forms a cyclopenteno ring therewith.

5. An acid-catalyzed, addition-rearrangement product of allyl alcohol and dicyclopentadiene, said product being an ether of allyl alcohol and hydroxydihydronordicyclopentadiene, in which the allyl nucleus is attached through oxygen to a secondary carbon atom flanked by a methylene group'and tertiary carbon atom in an endoethylene cyclopenteno group carrying a propenylene group which forms a cyclopenteno ring therewith.

6. An acid-catalyzed, addition-rearrangement product of oleyl alcohol and dicyclopentadiene, said product being an ether of oleyl alcohol and hydroxydihydronordicyclopentadiene, in which the oleyl nucleus is attached through oxygen to a secondary carbon atom in an endoethylene cyclopentano group carrying a propenylene group which forms a cyclopenteno ring therewith.

7. An. acid-catalyzed, addition-rearrangement product of an unsaturated cycloaliphatic alco hol and dlcyclopentadiene, said product being an ether of the unsaturated cycloaliphatic alcohol and hydroxydihydronordicyclopentadiene, in which the alcohol residue is attached through oxygen to a secondary carbon atom flanked by a methylene group and a tertiary carbon atom in an endoethylene cyclopenteno group carrying a propenylene group which forms a cyclopenteno ring therewith.

8. An acid-catalyzed, addition-rearrangement product of 2,5-endomethylene-A -tetrahydrobenzyl alcohol and dicyclopentadiene, said product being an ether of 2,5-endomethylene-A tetrahydrobenzyl alcohol and hydroxydihydronordicyclopentadiene, in which the 2,5-endomethylene-..\ -tetrahydrobenzyl nucleus is at of an acidic condensingagent.

and hydroxydihydronordicyclopentadiene. in which the alcohol residue is attached diene with said alcohol in the presence of a boron triiiuoride catalyst. e

14. A method for preparing ethers of hydroxydihydronordicyclopentadiene and an aliphatic alcohol having a double bond, which comprises reacting dicyclopentadiene and said alcohol in the presence of a boron triiluorlde catalyst.

15. A method for preparing ethers of hydroxydihydronordicyclopentadiene and an aliphatic alcohol having a double bond, which comprises reacting dicyclopentadiene and said alcohol in the presence of a catalyst consisting of a coordination complex of boron trifluoride and an oxygenated organic compound.

16. A method for preparing an ether of hydroxydihydronordicyclopentadiene and allyl a1- cohol, which comprises reacting dicyclopentadiene with said alcohol in the presence 01' an acidic condensing agent. v

17. A method for preparing an ether of hydroxydihydronordicyclopentadiene and an unsaturated cycloaliphatic alcohol, which comprises asoaeos reacting dicyclopentadiene with said alcohol in th: presence or an acidic condensing agent.

18. A method for preparing an ether of hydroxydihydronordicyclopentadiene and 2,5-endomethylene-A -tetrahydrobenzyl alcohol, which comprises reacting dicyclopentadiene with said I alcohol in the presence of an acidic condensing agent.

19. A method for preparing an ether of hydroxydihydronordicyclopentadiene and oleyl alcohol, which comprises reacting dicyclopentadiene with said alcohol in the presence of an acidic condensing agent.

- 20. The process of claim 16 wherein the catalyst is a boron tritluoride catalyst.

21. The process of claim 17 wherein the catalyst is a boron trifluoride catalyst.

22. The process of claim 18 wherein the catalyst is a boron trifluoride catalyst.

23. The process of claim 19 wherein the cata lyst is a boron trifluoride catalyst.

HERMAN A. BRUSON. 

